Process for producing polymer, the polymer, and curable composition comprising the polymer

Abstract

This invention provides method of producing a polymer which comprises substitution of carboxylic acid group for a terminal halogen group of a polymer obtainable by atom transfer radical polymerization. The carboxylic acid group may be a carboxylic acid salt group, more preferably a carboxylic acid potassium salt group. In carrying out the atom transfer radical polymerization in the practice of the invention, a transition metal complex can be used as a polymerization catalyst. The transition metal complex may be a transition metal complex with an element of the group 7, 8, 9, 10 or 11 of the periodic table as the central atom, more preferably a copper, nickel, ruthenium or iron complex and, in particular, a copper complex is used. The polymer obtainable by atom transfer radical polymerization is obtained by polymerization of a (meth)acrylic monomer, particularly the polymer obtained by polymerization of an acrylic acid ester monomer.

What is claimed is:  
     
       1. A method of producing a polymer 
       which comprises substitution of carboxylic acid group for a terminal halogen group of a polymer obtained by atom transfer radical polymerization,  
       said substitution of carboxylic acid group comprising using a carboxylic acid group-containing compound,  
       and said carboxylic acid group-containing compound being a polymer.  
     
     
       2. The method of producing a polymer according to  claim 1 , 
       wherein the carboxylic acid group is a carboxylic acid salt group.  
     
     
       3. The method of producing a polymer according to  claim 2 , 
       wherein the carboxylic acid salt group is a carboxylic acid potassium salt group.  
     
     
       4. The method of producing a polymer according to  claim 1 , 
       wherein the atom transfer radical polymerization is carried out using a transition metal complex as the polymerization catalyst,  
       said transition metal complex being a transition metal complex whose central metal is an element of the group 7, 8, 9, 10 or 11 of the periodic table of the elements.  
     
     
       5. The method of producing a polymer according to  claim 4 , 
       wherein the transition metal complex is a complex of copper, nickel, ruthenium or iron.  
     
     
       6. The method of producing a polymer according to  claim 5 , 
       wherein the transition metal complex is a copper complex.  
     
     
       7. The method of producing a polymer according to  claim 1 , 
       wherein the polymer obtained by atom transfer radical polymerization is obtained by polymerization of a (meth)acrylic monomer.  
     
     
       8. The method of producing a polymer according to  claim 7 , 
       wherein the (meth)acrylic monomer is an acrylic ester monomer.  
     
     
       9. The method of producing a polymer according to  claim 1 , 
       wherein the terminal halogen group of the polymer obtained by atom transfer radical polymerization is a secondary halogen group.  
     
     
       10. The method of producing a polymer according to  claim 1 , 
       wherein the polymerization is carried out in the presence of a nitrogen atom-containing compound.  
     
     
       11. The method of producing a polymer according to  claim 10 , 
       wherein the nitrogen atom-containing compound is selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines and heterocyclic nitrogen bases.  
     
     
       12. The method of producing a polymer according to  claim 10 , 
       wherein the atom transfer radical polymerization is carried out using an amine compound or pyridine compound as a ligand to the catalyst and using said ligand also as the nitrogen atom-containing compound.  
     
     
       13. The method of producing a polymer according to  claim 12 , 
       wherein the atom transfer radical polymerization is for polymerizing a vinyl monomer  
       and the carboxylic acid group substitution reaction is effected by adding a carboxyl-containing compound directly to the polymerization system.  
     
     
       14. The method of producing a polymer according to  claim 1 , 
       wherein the carboxylic acid group-containing compound has a carboxylic acid group in a side chain thereof.  
     
     
       15. The method of producing a polymer according to  claim 14 , 
       wherein a polymer obtained by the substitution reaction is a graft polymer.  
     
     
       16. The method of producing a polymer according to  claim 14 , 
       wherein a polymer obtained by the substitution reaction is a gel.  
     
     
       17. A method of producing a polymer 
       which comprises substitution of carboxylic acid group for a terminal halogen group of a polymer obtained by atom transfer radical polymerization,  
       said substitution of carboxylic acid group comprising using a carboxylic acid group-containing compound,  
       and said carboxylic acid group-containing compound having two or more carboxylic acid groups.  
     
     
       18. The method of producing a polymer according to  claim 17 , 
       wherein the carboxylic acid group is a carboxylic acid salt group.  
     
     
       19. The method of producing a polymer according to  claim 18 , 
       wherein the carboxylic acid salt group is a carboxylic acid potassium salt group.  
     
     
       20. The method of producing a polymer according to  claim 17 , 
       wherein the atom transfer radical polymerization is carried out using a transition metal complex as the polymerization catalyst,  
       said transition metal complex being a transition metal complex whose central metal is an element of the group 7, 8, 9, 10 or 11 of the periodic table of the elements.  
     
     
       21. The method of producing a polymer according to  claim 20 , 
       wherein the transition metal complex is a complex of copper, nickel, ruthenium or iron.  
     
     
       22. The method of producing a polymer according to  claim 21 , 
       wherein the transition metal complex is a copper complex.  
     
     
       23. The method of producing a polymer according to  claim 17 , 
       wherein the polymer obtained by atom transfer radical polymerization is obtained by polymerization of a (meth)acrylic monomer.  
     
     
       24. The method of producing a polymer according to  claim 23 , 
       wherein the (meth)acrylic monomer is an acrylic ester monomer.  
     
     
       25. The method of producing a polymer according to  claim 18 , 
       wherein the terminal halogen group of the polymer obtained by atom transfer radical polymerization is a secondary halogen group.  
     
     
       26. The method of producing a polymer according to  claim 18 , 
       wherein the polymerization is carried out in the presence of a nitrogen atom-containing compound.  
     
     
       27. The method of producing a polymer according to  claim 26 , 
       wherein the nitrogen atom-containing compound is selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines and heterocyclic nitrogen bases.  
     
     
       28. The method of producing a polymer according to  claim 26 , 
       wherein the atom transfer radical polymerization is carried out using an amine compound or pyridine compound as a ligand to the catalyst and using said ligand also as the nitrogen atom-containing compound.  
     
     
       29. The method of producing a polymer according to  claim 28 , 
       wherein the atom transfer radical polymerization is for polymerizing a vinyl monomer  
       and the carboxylic acid group substitution reaction is effected by adding a carboxyl-containing compound directly to the polymerization system.  
     
     
       30. The method of producing a polymer according to  claim 17 , 
       wherein substitution reaction is effected with a compound having two or more carboxylic acid groups, whereby the carboxylic acid groups are introduced into termini of the resulting polymer.  
     
     
       31. The method of producing a polymer according to  claim 17 , 
       wherein substitution reaction is effected with a compound having two or more carboxylic acid groups, whereby polymer molecules are coupled together.  
     
     
       32. A method of producing a polymer 
       which comprises substitution of carboxylic acid group for a terminal halogen group of a polymer obtained by atom transfer radical polymerization,  
       said substitution of carboxylic acid group comprising using a carboxylic acid group-containing compound,  
       and said carboxylic acid group-containing compound being obtained by reacting a cyclic acid anhydride with a functional group-containing alcohol.  
     
     
       33. The method of producing a polymer according to  claim 32 , 
       wherein the carboxylic acid group is a carboxylic acid salt group.  
     
     
       34. The method of producing a polymer according to  claim 33 , 
       wherein the carboxylic acid salt group is a carboxylic acid potassium salt group.  
     
     
       35. The method of producing a polymer according to  claim 32 , 
       wherein the atom transfer radical polymerization is carried out using a transition metal complex as the polymerization catalyst,  
       said transition metal complex being a transition metal complex whose central metal is an element of the group 7, 8, 9, 10 or 11 of the periodic table of the elements.  
     
     
       36. The method of producing a polymer according to  claim 35 , 
       wherein the transition metal complex is a complex of copper, nickel, ruthenium or iron.  
     
     
       37. The method of producing a polymer according to  claim 36 , 
       wherein the transition metal complex is a copper complex.  
     
     
       38. The method of producing a polymer according to  claim 32 , 
       wherein the polymer obtained by atom transfer radical polymerization is obtained by polymerization of a (meth)acrylic monomer.  
     
     
       39. The method of producing a polymer according to  claim 38 , 
       wherein the (meth)acrylic monomer is an acrylic ester monomer.  
     
     
       40. The method of producing a polymer according to  claim 32 , 
       wherein the terminal halogen group of the polymer obtained by atom transfer radical polymerization is a secondary halogen group.  
     
     
       41. The method of producing a polymer according to  claim 32 , 
       wherein the polymerization is carried out in the presence of a nitrogen atom-containing compound.  
     
     
       42. The method of producing a polymer according to  claim 41 , 
       wherein the nitrogen atom-containing compound is selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines and heterocyclic nitrogen bases.  
     
     
       43. The method of producing a polymer according to  claim 41 , 
       wherein the atom transfer radical polymerization is carried out using an amine compound or pyridine compound as a ligand to the catalyst and using said ligand also as the nitrogen atom-containing compound.  
     
     
       44. The method of producing a polymer according to  claim 43 , 
       wherein the atom transfer radical polymerization is for polymerizing a vinyl monomer  
       and the carboxylic acid group substitution reaction is effected by adding a carboxyl-containing compound directly to the polymerization system.  
     
     
       45. The method of producing a polymer according to  claim 32 , 
       wherein the functional group is selected from the group consisting of alkenyl, hydroxyl, amino and epoxy groups.  
     
     
       46. The method of producing a polymer according to  claim 32 , 
       wherein the cyclic acid anhydride is selected from the group consisting of succinic anhydride, phthalic anhydride and glutaric anhydride.  
     
     
       47. The method of producing a polymer according to  claim 46 , 
       wherein the cyclic acid anhydride is phthalic anhydride.